Lubricating composition



lubricating oil composition.

United States Patent F 3,309,317 LUBRHCATING COMPOSITION Eugene Wittner, Florissant, Mo, and Bobby W. Maionc, East Alton, 11L, assiguors to Shell Oil Company, New York, N.Y., a corporation of Delaware No Drawing. Filed June 8, 1964, Ser. No. 373,512 3 Claims. (Cl. 25249.9)

This invention relates to stable lubricating oil compositions which possess excellent detergent as well as wear and corrosion resistant properties.

It is known that a wide variety of oil-soluble nitrogencontaining polymers are useful as detergents in lubricating compositions. Polymers of this type such as copolymers of long-chain alkyl acrylates and polymerizable compounds containing basic amino or amido or imidoamino groups such as copolymers of C1048 alkyl methacrylates and vinyl pyridine or vinyl pyrrolidone or poly(alkenyl)succinic anl'iydride-polyalkylene polyamine reaction products and the like, function effectively as detergents for only short durations when used in engines operating for long periods under severe temperatures and pressures. Under such conditions they tend to break down, lose their detergent properties and form sludge, and cause corrosion and wear of engine parts. Attempts to improve these non-ash forming polymeric detergents by modifying them or by addition of auxiliary agents such as organic phosphate esters or salts thereof, bisphenols or thiophenols has resulted in some improvement particularly when such lubricants are used in engines operating for short durations under mild conditions of temperature and pressure. However, under severe engine operating conditions over long periods of use these classes of inhibitors or even other types such as arylarnines, organic thiophosphates and the like, fail to improve non-ashforming polymeric detergent-containing lubricants so as to meet required standards of 6000 mile drains and various specification requirements.

It is an object of the present invention to provide an improved non-ash forming lubricating oil composition. It is another object of the invention to provide an improved detergent lubricant possessing good stability and anti-wear properties. Still another object of the invention is to provide a corrosion resistant non-ash forming Other objects will become apparent during the following description of the invention.

It has now been found that compounded lubricants containing ash-less nitrogen-containing polymeric detergents can be greatly improved with respect to increased detergent life, stability and sludge, corrosion, and wear inhibition by incorporating therein minor amounts each of (I) an oil-soluble alkaryl phosphoramide having the formula where R is an alkyl radical of from 1 to 18 carbon atoms, preferably 414 carbon atoms, R is hydrogen, or a hydrocarbyl radical e.g. alkyl, aryl, cycloalkyl radical, X is oxygen or sulfur, go is a mono or polyaryl radical and x and y each represent integers the sum of which is 3 and preferably such that x is 2 and y is 1, and (11) an oil-soluble diaryl compound represented by the formula Y Y (II) where (p is a monoor polyaryl radical e.g. phenyl or naphthyl radical, R" is a C a-lkyl radical, Y is OH or 3,309,317 Patented Mar. 14, 1967 where R is the same as in Formula I, Z is CH O, or S and n is an integer of from zero to 2 and is preferably 2 when Y is OH and zero when Y is Preferred class of compounds are oil-soluble bisphenols represented by formula where the Rs are C4 Cg tertiary alkyl groups preferably in the 2,6, 2,6 positions and (HE) an oil-soluble polyaryl polyamine represented by the formula:

(IIB) where Z is oxygen, sulfur, or a methylene radical and R is hydrogen or a C alkyl radical such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, amyl, hexyl, octyl, radicals or mixtures thereof.

The alkaryl phosphoramides as represented by formula (I) and preferably by formulas where R is the same as defined in Formula I, can be prepared by any suitable means such as are described in chapter 10 of Kosolapoffs text entitled, Organo Phosphorus Compounds. A specific illustrative example for the preparation of such a compound is as follows:

Example A .-Bis(n0nylp henyl) phosphoramidate A solution of 104.1 g. (0.2 mole) of -bis(nonylphenyl) phosphorochloridate in 300 ml. of benzene was placed in a 1-liter flask equipped with a mechanical stirrer, a thermometer, a reflux condenser and a gas inlet tube. The mixture was stirred and cooled to 5 C. in an ice bath. Gaseous ammonia was admitted to the flask above the liquid level (to avoid plugging the gas inlet with precipitated ammonium chloride). The mixture was stirred and cooled and the rate of the addition of am- .monia was controlled so that the pot temperature remained below 15 C. When no more ammonia was absorbed, the addition of ammonia was discontinued and the reaction mixture was refluxed for one hour. The flask contents were cooled, the precipitate was removed by filtration using Celite filter aid, the filtrate was washed three times with water and the benzene solution was dried over anhydrous magnesium sulfate. The benzene was removed under vacuum and the residue was topped at ca 100 C. and 1 mm. Hg until the last traces of solvent were eliminated. A total of g. of product (85% w. of theory), a very viscous yellow oil, was obtained. 7

Found, percent weight: C, 71.3; H, 9.83; P, 6.22; N, 2.35. M01. wt., 600. Calculated for C 'H O NP,

percent weight: C, 71.8; H, 9.67; P, 6.18; N, 2.79. M01. wt., 501.

Other examples of phosphoramides prepared essentially by the method described include:

Example B: Bis(isobutylphenyl)phosphoramide Example C: Bis(diisobutylphenyl)phosphoramide Example D: Bis(dodecylphenyl)phosphoramide Example E: Bis(octadecylphenyl)phosphoramide Example F: Bis(nonylnaphthyl)phosphoramide Example G: Bis(nonylphcnyl)thionophosphoramide Example H: Bis(diisobutylphenyl)thionophosphoram ide Example I: Nonylphenylphosphordiamide Example I: Dodecylp'henylphosphordiarnide Example K: Nonylphenylthionophosphordiamide Example L: N,N-butyl bis(nonylphenyl)phosphoramide Example M: N,N-butyl bis(nonylphenyl)thionophosphoramide Example N: N,N-butylnonylphenylphosphordiamide Example N-isopropyl his(octylphenyl)phosphoramide Example P: N-methyl bis(octylpheny1)thionophosphoramide The compounds of Formula II when 2 is CH and Y is OH as represented by the Formula HA and 1113 are illustrated by the following examples: 1,1-bis(3,5-ditertiarybutyli-hydroxyphenyl) methane, 1,1-bis(3,5-diisoproproyl 4-hydroxyphenyl)methane, 1,l-bis(3,5-di-secbutyl 4-hydroxyphenyl)methane; 1,1-bis(3-isopropyl-5- tertiarybutyl 4-hydroxyphenyl) methane; 1,1-bis[3,5-di(2- octyl) 4-hydroxyphenyl} methane; 1,1-bis[3-sec-butyl-5 (2 'hexyl) 4-hydroxyphenyl]methane; 1,l-bis(2-tert-butyl- S-methyl-Z-hydroxyphenyl)methane and mixtures thereof.

The polyaryl polyamine compounds represented by Formula IIB include (a) bis(N,N-dialkylarninophenyl)- methane and (b) bis(N,N-dialkylaminop'henyl)ether or thioether. The compounds of (ILBa) can be prepared by suitable means such as by reacting N,N-dialkyl aniline in an acid medium and adding formaldehyde to the reaction at low temperature of below 40 C. and thereafter allowing the reaction to increase to 60150 C. for several hours after which the end product is recovered. In the reaction it is preferred that an excess of 40-100% of the amine be used. Thus, bis(N,N-dimethylaminophenyl)methane was prepared by adding 3 moles of N,N' dirnethyl aniline and 1 mole of formaldehyde solution) to hydrochloric acid at 6075 C. and the mixture heated for 1-2 hours after which the end product was recovered. Other examples include: bis-(N,N-diethylaminophenyl)methane, bis(N,N-dipropylaminophenyl)- methane, bis(N,N-dibutylaminophenyl)methane, bis(-N- secondarybutylaminophenyl)methane, bis(N,N-diamylamino phenyl methane, bis (N,N-dioctylam-inophenyl) methane. The ether or thioethers of (IIBb) include his- (N,N-dimethylaminophenyl)ether, bis(.N,N-dip-ropylaminophenyl)ether, bis(N-secondarybutylaminophenyl)ether, bis(N,N-diocty1aminophenyl)ether and their thioether derivatives. Preferred compounds are bis(N-secondarybutylaminophenyl)ether and bis(N-secondarybutylarninophenyl)methane.

The detergent polymers which coact with the phosphoramides of Formula I and compounds IIA or IIB or mixture thereof are derived from nitrogen-containing polymerizable monomers containing primary, secondary or tertiary (the latter two are preferred) amino nitrogen, including heterocyclic amino-containing substances, having an ethylenically unsaturated polymerizable group. These detergent polymers may be obtained by polymerizing vinyl substituted 'heterocyclic amino nitrogen-containing substances such as vinyl pyridine, or polyamines prepared by reducing, in the presence of ammonia or primary or secondary amines, with polymerizable unsaturated alcohols, acids of esters such as acrylate and methacrylates of long-chain fatty acids, and the like. The preferred polymeric amino compounds are those containing tertiary amine groups and particularly those containing heterocyclic amino groups such as obtained by copolymerizing a polymerizable heterocyclic nitrogen base compound with a polymerizable unsaturated material free of heterocyclic nitrogen-containing radicals which can be illustrated by: copolymers of stearyl methacrylate, lauryl methac'rylate and Z-methyl-S-vinyl pyridine; and those which contain additional C alkyl methacrylates in the polymer, such as copolymers of stearyl methacrylate, lauryl methacrylate, methyl methacrylate and Z-methyl-S-vinyl pyridine; and similar copolmers in which the methyl methacrylate is replaced by butyl methacrylate and 2-methyl-5-vinyl pyridine is replaced by 5 ethyl 2 vinyl pyridine. Other suitable polymeric amine detergents are copolymers of C alkyl acrylates, e.g. lauryl methacrylate and aminoalkyl acrylates, e.g. diethylaminoethyl methacrylate. Also suitable are vinyl pyrrolidone-containing polymers or similar copolymers as described in Belgian Patent 550,442 and British Patent 808,664 and mixtures thereof. Acrylate-vinyl pyrrolidone and copolymers are sold by Rohm & Haas under the designations Acryloid 315K or 917 or 966 and are copolymers of N-vinyl pyrrolidone and lauryl methacrylate of varying molecular weights such as 50,000 to over 2 million, preferably between 400,000 and 800,000 as determined by the light scattering method.

Still another class of basic amino nitrogen-containing detergent polymers are polymeric amino-imide-containing detergents such as N-dialkylamino alkyl alkenyl succinimides and illustrated by N-dimethylaminopropyl polybutenyl succinimide, or tetraethylene pentamine derivative of polybutenyl succinic anhydride and the like in the molecular Weight range of 1500 to 5,000.

Preferred copolymers having good detergency are: l) copolymer of 30% stearyl methacrylate, 51% lauryl meth acrylate, 14% methyl methacrylate and 5% Z-methyl-S- vinyl pyridine (M.W.=600,000, N=0.02%; (2) copolymer of lauryl methacrylate/stearyl methacrylate/2- methyl-S-vinyl pyridine (M.W.=800,000, N=0.6%; (3) copolymer of lauryl methacrylate/stearyl methacrylate/4- vinyl pyridine (M.W.=600,000, N=0.8%); (4) copolymer of lauryl methacrylate/S ethyl 2 vinyl pyridine (M.W.=200,000, N=2.8%); (6) copolymer of lauryl methacrylate/vinyl pyrrolidone (M.W.=450,000); (7) imide of diethylene triamine and polybutenyl succinic anhydride; (8) imide of tetraethylene pentamine and mono(polyisobutylene)succinic acid; (9) tetraethylene pentamine diimide of m0no(polyisobutylene) succinic acid; (10) imide of tetraethylene pentamine and mono (polypropylene)succinic acid and mixtures thereof. In examples (8) and (9) the polyisobutylene ranged in molecular weight (M.W.) from 1500-3000 and in example (10) the polypropylene ranged in M.W. from 8004500.

The phosphoramides (I) and the bisphenol (IIA) or polyaryl polyamine (HE) and the detergent polymers can each be used in concentrations of from about 0.01% to about 10%, preferably between 0.1% and 5% by weight.

When desired, additional improvements can be in1- parted to the oil compositions containing the polymer salts of this invention by incorporating small amounts (0.01%- 2%, preferably 0.1%-1%) arylamines such as phenylalpha-naphthylamine, P S -terpene reaction products, sulfurized fatty oils and derivatives thereof, e.g. surfurized sperm oil, sulfurized oleic acid and the like.

Lubricating oils for additives of this invention can be any natural or synthetic material having lubricating properties. Thus, the base maybe a hydrocarbon oil of wideviscosity range, e.g. SUS at 100 F. to SUS atv 210 F. The hydrocarbon oils may be blended synthetic lubricants such as polymerized olefins, organic esters of organic and inorganic acids, e.g. di-Z-ethylhexyl 6' sebacate, pentaerythritol esters of mixed C fatty acids; Composition F: Percent wt. polyalkyl silicone polymers, e.g. dimethyl silicone poly- Copolymer of Ex. 8 2 mer, and the like. If desired, the synthetic lubricants ExampleA 0.5 may be used as the sole base lubricant. 1,l-bis(3,5-ditertiarybutyl-4-hydroxyphenyl) Mineral lubricating oils which are particularly desira- 5 methane 0.75 ble for use in compositions of this invention were ob- Ester base lubricant (95% of dipentaerythritol tained from West Texas Ellenburger crudes, East Texas ester of a mixture of C aliphatic nionocarcrudes, Oklahoma crudes, California crudes. A useful boxylic acids and 5% of pentaerythritol ester refined oil therefrom has the following properties: of C fatty acid) B L Gravity, API, min 26.5 10 Composition Gr Pour point, F., max l0 Copolymer of 6 5 Flash, 000, u R, min. 390 Example I 1 Viscosity, sUs t 100 F, 120.160 tyl minophenyl)methane 1 Viscosity index, min 95 E t r base lubricant (95% of dipent-aerythritol ester of a mixture of C aliphatic monocar- Another suchr 111.15 a SAE 30 mineral oil having the boxylic acids and 5% of psntaerythritol ester followlng propeltles of c acid) Bal Gravlty, a The mixtures Of phosphoramides and bisphenol or the Point I polyaryl polyamino compounds of this invention are ext 9 5 cellent stabilizers as evidenced from the data presented bei i at 210 F lOW. In the tests below the effectiveness of lubricants of Viscosity 50- O the present invention formaintainin lon dispersant or Preferred compositions of this invention are illustrated ergent life was determined by subjecting the test comby th f ll i examples, 25 position to the Air Oxidation test developed by the Shell Composition A; P e t t, Development Company to simulate engine operating con- Copolymer of Ex. 8 2 Cli iOHS under Which maximum sludge forms and com- Example A 0.5 prises blowing air through the test oil composition at the l,l-bis(3,5-ditertiarybutyl-4-hydroxyphenyl) rate of 5 liters per hour at 300 F. removing samples at methane 0.5 regular intervals and determining the dispersant or used Mineral lubricating oil (HVI SAE 30) Bal. detergent life of the oil by the method described in U.S. C iti B; Patent 2,770,530, and the results shown in Table I were Copolymer of Ex. 8 2 as f ll W I TABLE I.AIR OXIDATION TEST [300 F., 20 ppm. Cu, 20 ppm. iron] Composition Induction Oxidation Disperscucy Period, Hrs. Time, Hrs. Lite, Hrs.

(1) Mineral lubricating oil (HVI 100 neutral) 0 3 10 (2) Mineral lubricating oil (I'IVI 100 neutral) plus 0.5% 1,l-bis(3-5-clitertiarybutyl-4- hydroxy henyl)-rnetha ne 9 15 1g (3) Mineral lubricating oil (HVI 100 neutral) plus 0.5% 1,l-bis(3,5-ditertiarybutyl4- hydroxyphenyl)-methane plus 2% copolymer of Ex. 8 .u 33 38 3g (4) Mineral lubricating oil (HVI 100 neutral) plus 0.5% bis(N-seebutylaminophenyl)- methane 5 11 6 (5) Mineral lubricating oil (HVI 100 neutral) plus 0.5% bis(N-sec-butylaminoplienyD- methane plus 2% eopolymer of Ex. 8 1 5 l0 (6) ComposiiionA 240 240 240 (7) Composition B 240 240 240 1 Time to absorb 1 millimole OQIgram sempie.

Example A 0.5 Compositions of the present invention also offer excel- Bis(N-sec-butylaminophenyl)methane 0.5 lent corrosion protection as evidenced from the 40 hour Mineral lubricating oil (HVI SAE 30) Bal. CLRL-38 engine test shown in Table II.

Composition C: TABLE II Copolymer of EX 8 5 [Base Oil; HVI SAE 30 +471; Copolymer of EX, 8] Example A 0.5 Bis(N-sec-butylaminophenyl)ether 0.5 Cl1Pb bearing Mineral lubricating oil (HVI SAE 30 Bat. Addltlves= wt. loss, Dig/hi Composition D: (1) g 73 Copolymer f EX 1 5 6D (2) 0.0% 1,1-b1s(3,5-dltertrarybutyl-4-hydroxy- ExampleA 0,5 phenynmfithane 22 1,Lbis(3,5 ditertiarybutyl 4 hydroxyphenyl) (3) 0.5% bis(nonylphenyl)phosphoramidate 100 methane 5 (4) 0.5% l,1-bis(3,5-ditertiarybutyl-4-hydrox Mineral lubricating oil row-3o Bal. phenyllmethane 05% bismonylrihenyll Composition E; phosphoramldate 6 Copolymer 0f 1 5 Other additives may also be incorporated into the in- EXample B bricating composition according to the invention, for ex- 1,l-bis(3-5-ditertiarybutyl-4-hydroxyphenyl) ample, anti-foaming agents, e.g. silicone polymers; vismethane 0.5 cosity index improvers, for example, polymeric acrylic Mineral lubricating oil (SAE 20) Bal. esters of the Arcyloid and 710 class; extreme pressure additives, such as dibenzyl disulfide, sulfurized sperm oil, sulfurized oleic acid; oiliness agents, such as a-cidless tallow, oleic acid and the like.

Compositions of this invention can be used as engine lubricants, hydraulic fluids, industrial lubricants and fuels, greases and the like.

We claim as our invention:

1. A lubricating oil composition comprising a major amount of lubricating oil and from 0.01% to about 10% each of:

(1) an amino-imide of a mono C polymeric hydrocarbyl succinic anhydride;

(2) a compound selected from the group consisting of a bis(ditertiaryalkyl 4 hydroxyphenyl)methane wherein each of the tertiary alkyl radicals has from 4 to 8 carbon atoms and a bis(N,N-dialkylaminophenyDmethane wherein each of the alkyl radicals has from 1 to 8 carbon atoms; and

(3) a bis(alkylphenyl)phosphoramide wherein each alkyl radical has from 4 to 14 carbon atoms.

2. A lubricating oil composition comprising a major amount of lubricating oil and from about 0.01% to about 10% each of an oil-soluble polymeric detergent of an amino-imide of a mono C polymeric hydrocarbyl succinic anhydride and a mixture of bis(3,5-ditertiarbybu- 8 tyl-4-hy-dr0xyphenyl)methane and bis(nonylphenyl)phosphoramide.

3. A lubricating oil composition comprising a major amount of lubricating oil and from about 0.01% to about 10% each of an oil-soluble polymeric detergent of an amino-imide of a mono C polymeric hydrocarbyl succinic anhydride and a mixture of bis(N,N-dimethylamigophenynmethane and bis(nonylphenyl)phosphorami e.

References Cited by the Examiner UNITED STATES PATENTS 2,146,584 2/1939 Lipkin 25249.9 2,151,380 3/1939 Flint et al 25249.9 2,290,860 7/1942 Burk et al 25249.9 2,385,713 9/1945 Kosolapoff 260-959 2,944,086 7/1960 Coffield et al 25252 3,219,666 11/1965 Norman et al 2425l.5

FOREIGN PATENTS 760,554 10/1956 Great Britain. 808,665 2/1959 Great Britain.

DANIEL E. WYMAN, Primary Examiner.

25 L. G. XIARHOS, Assistant Examiner. 

1. A LUBRICATING OIL COMPOSITION COMPRISING A MAJOR AMOUNT OF LUBRICATING OIL AND FROM 0.01% TO ABOUT 10% EACH OF: (1) AN AMINO-IMIDE OF A MONO C20-300 POLYMERIC HYDROCARBYL SUCCINIC ANHYDRIDE; (2) A COMPOUND SELECTED FROM THE GROUP CONSISTING OF A BIS(DITERTIARYALKYL - 4 - HYDROXYPHENYL)METHANE WHEREIN EACH OF THE TERTIARY ALKYL RADICALS HAS FROM 4 TO 8 CARBON ATOMS AND A BIS(N,N-DIALKYLAMINOPHENYL)METHANE WHEREIN EACH OF THE ALKYL RADICALS HAS FROM 1 TO 8 CARBON ATOMS; AND (3) A BIS(ALKYLPHENYL)PHOSPHORAMIDE WHEREIN EACH ALALKYL RADICAL HAS FROM 4 TO 14 CARBON ATOMS. 